Aryl-amino alkenyl phenols



Patented June. 24, 1941 2,246,924 ARR-AMINO ALKENYL PHENOLS Philip "1. Paul, Naugatuck, Coma, assignor to Unitedv States Rubber Company; New York, N. Y., a corporation of New Jersey No Drawing. Application June 28, 1939, Serial No. 281,529

8 Claims. (Cl. 260-571) The present invention relates to new chemicals, Analysis referred to as aryl-amino alkenyl phenols. 1 mt s 8142 They are definite chemical entities and are bclieved to have the general formula r Theory "per cent 623 H OH Found do 6.23 M N EXAMPLE IL-Preparation of 2-methallyl 4-ani- A lino phenol 4-methallyloxy diphenylamine was heated over where N s nitrogen; H is hydrogen; 015 Oxygen; night at 212 c. in a sealed tube. The tube was Ar refers to an aryl nucleus of the benzene, naphopened and the contents dissolved in benzene and thalene or biphenyl series; A is an alkenyl group. washed with 30% potassium hydrx1de Acldb The aryl nucleus may also contain substituents fi ation f t alkaline t t yielded g 2- such as halogen, hydroxyalkyl. aryl, amino, methallyl 4-anilino phenol M. P. IOU-102 c. ondary alkyl amino, tertiary alkyl amino, al-

v Analysis lzfinggxgcanihno, mercapto, tertiary aryl ammo, Nitrogen: Per cent Illustrative of such compounds are the folg g lowing: Dun

The alkenyloxy diarylamine may be first prepared by reacting a C-hydroxy diarylamine with an alkenyl chloride.

The present chemicals may be used for various purposes, for example, as insecticides, pharmaceuticals, intermediates for the preparation of other chemicals. high pressure lubricants, gasoline inhibitors, rubber antioxidants, etc. For example, it has been found that 2-allyl 4-anilino phenol is an excellent rubber antioxidant. To a portion of rubber master batch having the composition (parts are by weight) 2-allyl 4-anilino phenol Z-rnethallyl 4-anilino phenol Z-methallyl S-anilino phenol 2-allyl fi-anilino phenol 3-allyl 4-anilino phenol 2-allyl 4-naphthylamino phenol 2-allyl '4-tolylamine phenol 2-allyl 4-xenylamino phenol 2-methallyl i-- (p-anilinc anilino) phenol Z-propenyl -i-anilino phenol 1 3-isobutenyl 4-anilino phenol 3-propenyl 4-naphthylamino phenol 2-isobutenyl 4-xenylamino phenol Smoked Sheets 100. 4-butenyl 3-ani1ino phenol Ca bon black 47. 2-isobutenyl 4-anillno phenol nc Oxide 5. 2-vinyl 4-anilino phenol e ta 3.50 3-viny1 4-naphthylamino phenol Zinc salt of cocoanut oil fatty acids 3.50 4-vinyl 3-anilino phenol u u 3.00 Th hemi al may be prepared by heating a Mercaptobenzothlazole C-alkenyl oxy-substitutecl diarylamine at an ele- 40 163 00 vated temperature, the following examples being 1 part of 2 any] 4 aniuno phenol was added elv s 111115?! whom Cures were made for 45, 60, '75 and 90 minutes at EXAMPLE I.-Prepamtion of Z-allyl 4-am'lm0 30 pounds steam The percent remaining tensile phenol before and after aging under 300 pounds oxygen 4-allyloxy diphenylamine (25 grams) was at 70 C. is as follows: heated for '7 minutes in a bath held at 240-250 C. During the heating, a vigorous reaction 00- Anticurred as evidenced by the fact that the tempera- Blank fggi ture of the 4-allyloxy diphenylamine rose to 285 C. The material was then vacuum distilled and the fraction boiling at 175-185 C. at 3 mm. was

Unaged 100 100 Aged 48 62 collected. On standing over night it crystallized. The 2-allyl 4-anilino phenol was purified by re- Where the term "rubber is used herein it is crystallization from a benzene-ligroin mixture. to be construed broadly as including caoutchouc.

The antioxidant maybe incorporated "in any" type of rubber composition, such as those used for automobile tires and tubes, hose, belting, sheet and thread rubber, rubberized fabrics, molded goods, boots and shoes, etc., whether vulcanized in a mold, in open steam, in hot air, or in the cold by the so-called acid process. The proportion of the antioxidant may vary from about 0.1% to 5%, although either smaller or greater proportions may be found useful. If the material to which it is added is a liquid such as rubber cement or an oil, the antioxidant may be dissolved therein in a suitable small proportion. The antioxidant may be incorporated into solid substances by milling or mastication, and prepared for incorporation into dispersions or solutions either in powder, paste or solution form, or applied in such forms for incorporation by diffusion, to the surfaces of vulcanized or unvulcanized rubber goods.

2,246,924 I Having thus described my invention, what'I claim and desire to protect by Letters Patent is:

1. An aryl-amino alkenyl monohydric phenol of the benzene series in which the alkenyl and hydroxy group are attached to the same benzene nucleus.

2. An aryl-amino Z-alkenyl monohydric phenol of the benzene series in-which the alkenyl and hydroxy; group are attachedftofthe same .benzene nucleus.

3. An aryl-amino 3-alkenyl monohydric phenol of the benzene series in which the ,alkenyl and hydroxy group are attached to the same benzene nucleus.

r 4. An-;aryl-amino"monohydric phenol of the benzene series having an allyl group ortho to the hydroxy group.

5. An anilino monohydric phenol of the benzene series having an allyl group ortho to the hydroxy group.

6. A compound which is a monohydric phenol of the benzeneseries having separately attached to the same benzene nucleus an alkenyl group and an aryl-amino group.

7. 2-allyl-4-ani1ino phenol.

8. 2-methallyl 4-anilino phenol.

PHILIP '1'. PAUL. 

